CARBON COMPOUNDS II

Course Outline

* HALOALKANES

- Nomenclature of the haloalkanes

* Synthetic utility of substitution reaction on haloalkanes e.g. with—

OH,_CH etc

* Importance and dangers of some organo — chlorine compounds e.g.

DDT, PCBs, PVC, CFCs

ALKANOLS

* General molecular formula and nomenclature

* Industrial preparation of ethanol by fermentation and from ethene

* Industrial and domestic uses of alkanols

ALKANOLS ACIDS

* General molecular formula and nomenclature

* Properties of natural occurring acids such as ethanoic and citric acids

* Test for the carboxylic functional group

AMINES AND AMINO ACIDS

* Classes of amines and their nomenclature

* Acidic and basic properties of amino acids that amino acids have acidic
and basic properties

* Relationship of amino acids to protein

SYNTHETIC MACRO MOLECULES

* Definition of polymerization

* Nature and uses of an addition and condensation polymers e.g.

polythene, polyamides and polyesters
1.0 HALOHYDROCARBONS (HALOALKANES)

INTRODUCTION

Haloalkanes are halogen derivatives of alkanes. Mono haloderivatives

(alky/halides) have a general molecular formular

Cn H2n+1 x or simply R — X where

R represents an alkeyl group and X the halogen member.

e.g. CH3CI Chloromethane

(Methyl chloride)

CH3CH2Br Bromoethane

(Ethyl bromide)
CH3
2-Iodopropane
CHI (Isopropyl iodide)
CH3

They may be classified into primary, secondary or tertiary according to the

nature of the carbon atom to which the halogen atoms is attached.
NOMENCLATURES

Both common and TUPAC names are in general usage nowadays, although the
TUPAC system which considers the compounds as halo – substituted alkanes
is gradually becoming the more popular.

The table below shows some common haloakanes, their formula and the IUPAC
name.

PHYSICAL PROPERTIES

Because of the polarity of the carbon — halogen bond, which enhances dipole
— dipole interaction in the liquid phase, haloalkanes have some what higher
boiling points than alkanes of comparable relative molecular mass.

Most haloalkanes are liquids, their boiling points depending upon the nature of
the alkyl groups and the halogen atom, although the halomethanes (apart from
iodomethane) fluoroethane and chloroethane are gases.
For corresponding halogen atoms, boiling points increase with increasing
relative molecular mass. Densities in the same order, this is accounted for in
terms of the closer packing of the smaller molecules in the liquid phase.
Bromo, and lodo alkanes are all denser than water

For corresponding alkyl groups,. The boiling points increase in the order fluoro
< chloro< bromo< iodo

SYNTHETIC PREPARATION OF HALO ALKANES

Substitution of Alcohols

The chloroalkane can be prepared by saturating the alcohol with dry hydrogen
chloride which is bubbled through it in the presence of a zinc chloride catalyst
and then refluxing on a water batt.

HCl CH 3 CH 2 CL+ H 2 0
( dry )⃗ZnCl 2 ( chloroethane )
CH3CH2OH + reflux

Chlorination of alcohols can also be brought about by refluxing with sulphur

dichloride oxide (thionyl chloride) SOd2 in the presence of a small amount of
pyridine C5H5N which absorbs the hydrogen chloride as it is formed.

CH 3 CH 2 0 H +SOCl2 ⃗
C 5 H 5 N CH 3 CH 2 Cl+S 02 +HCl
IMPORTANCE AND DANGERS OF SOME ORGAN — CHLORINE
COMPOUNDS E.G.B DDT, PCBs PVC, CFCs

An organochloride, organochlorine, chlorinated hydrocarbon or

chlorinated solvent is an organic compound containing at least one covalently
bonded clorine atom. Their wide structural variety and divergent chemical
properties lead to a broad range of application. Many derivatives are
controversial because of the effects of these compounds on the environment
and on human animal health.

Physical Properties

Chloride substituent’s modify the physical properties of organic

compounds in several ways. They are typically denser than water due to the
presence of high atomic weight of chlorine.

DDT (dichlorodiphenyltrichloro ethane)

Is an organochlorine insecticide which is a white, crystalline solid,

tasteless and almost odour.ess DDT is similar in structure to the insecticide
methoxychlor and acaricide dicofol. It is a highly hydrophobic, nearly insoluble
in water but has a good solubility in most organic solvent, fats and oils. DDT
does not occur naturally but is produced by the reaction of CCI 3CHO with
chlorobenzene (C6H5Cl) in the presence of sulphuric acid which acts as a
catalyst.

Environmental Impact

DDT is a persistent organic pollutant that is readily absorbed to soils and

sediments, which can act both at sinks as long — term sources of exposure
contributing to terrestrial organisms.

Depending on conditions, its soil half life can range from 22 days to 30
days. Routes of loss and degradation include run off, volatilization, photolysis
and aerobic and anaerobic biodegradation. Due to hydrophobic properties, in
aquatic ecosystems DDT and its metabolites are absorbed by aquatic
organisms and absorbs on suspended particles living little DDT dissolved in
the water itself. Its breakdown products and metabolitites dichlorodiphanyl
dichloroethane (DDE) and dichlorodiphenyl dichloroethylene (DDI) are also
highly persistent and have similar chemical and physical properties. DDT and
its breakdown products are transported from warmer regions of the world of
the Arctic by the phenomenon of global distillation where they then accumulate
in the region’s food web.
 Because of its lipophilic properties, DDT has a high potential to
bioaccumulate, especially in predatory birds. DDT, DDE and DDD magnify
through the food chain with apex predators such as raptor birds concentrating
more chemicals than other animals in the same environment. They are very
lipophilic and are stored mainly in body fat. DDT and DDE are very resistant to
metabolish in humans, their half — lives are 6 and up to 10 years respectively.

In the US, these chemicals were detected in almost all human blood
samples tested by the centres for disease control in 2005, though their lives
have sharply declined since most uses were banned in the US. This same
measured can equally be adopted in Nigeria.

Effects on wildlife and eggshell thinning

DDT is toxic to a wide range of living organisms, including marine

animals such as crayfish, daphnids, sea shrimp and many species of fish. It is
less toxic to mammals, but may be moderately toxic to some amphibian
species, especially in the larval stage. DDT, through its metabolite DDE,
caused eggshell thinning and resulted in severe population declines in multiple
North American and European bird of prey species. Eggshell thinning lowers
the reproductive rate of certain bird species by causing egg breakage and
embryo death. DDE related eggshell thinning is considered a major reason or
the decline of the bald eagle, brown pelican, peregrine falcon, and osprey.
However, different groups of birds vary greatly in their sensitivity to these
chemicals. Birds of prey, waterfowl, and song birds are more susceptible to
eggshell thinning than chickens and related species, and DDE appears to be
more potent than DDT. Even in 2010, more than forty years after the US ban,
California condors which feed on sea lions at Big Sur which in turn feed in the
Palos Verdes Shelf area of the Montrose Chemical Superfund site seemed to be
having continued thin-shell problems. Scientists with the Ventana Wildlife
Society and others are intensifying studies and remediations of the condors’
problems.

The biological thinning mechanisms is not entirely known, but there is

strong evidence that DDE inhibits calcium ATPase in the membrane of the
shell gland and reduces the transport of calcium carbonate from blood into the
eggshell land. This results in a dose-dependent thickness reduction. There is
also evidence that DDT disrupts female reproductive tract development,
impairing eggshell quality later. Multiple mechanisms may be at work, or
different mechanisms may operate in different species. Some studies show that
although DDE levels have fallen dramatically, eggshell thickness remain 10-12
percent thinner than before DDT was first used.

EFFECTS ON HUMAN HEALTH

Potential mechanisms of action on humans are genotoxicity and

endocrine disruption. DDT may be directly egnotoxic, but may also induce
enzymes to produce other genotoxic intermediates and DNA adducts. It is an
endocrine disruptor; the DDT metabolite DDE acts as an antiandrogen (but not
as an estrogen) DDT, DDTs main components, has little or no androgenic or
estrogenic activity. Minor component DDT has weak estrogenic activity.

Acute toxicity

DDT is classified as “moderately toxic” by the United States National

Toxicology Program (NTP) and “moderately hazardous” by the World Health
Organization (WHO), based on the rate oral LD50 of 113 mg/kg DDT has on
rate occasions been administered orally as a treatment or barbiturate
poisoning.

Chronic toxicity

Diabetes

DDT and DDE have been linked to diabetes. A number of studies from
the US, Canada, and Sweden have found that the prevalence of the disease in a
population increases with serum DDT or DDE levels.

Developmental Toxicity

DDT and DDE, like other organochlorines, have been shown to have
xenoestrogenic activity, meaning they are chemically similar enough to
estrogens, to trigger hormonal responses in animals. This endocrine disrupting
activity has been observed in mice and rat toxicological studies, and available
epidemiological evidence indicates that these effects may be occurring in
humans as a result of DDT exposure. The US Environmental Protection Agency
states that DDT exposure damages the reproductive system and reduces
reproductive success. These effects may cause developmental and reproductive
toxicity.

• A review article in The Lancet states, “research has shown that exposure
to DDT at amounts that would be needed in malaria control might cause
preterm birth and early weaning... toxicological evidence shows
 endocrine — disrupting properties; human data also indicate possible
disruption in semen quality, menstruation, gestational length, and
duration of lactation”.

• Human epidemiological studies suggest that exposure is a risk factor for

premature birth and low birth weight, and may harm a mother’ ability to
breast feed. Some 21st century researchers argues that these effects may
increase infant deaths, offsetting any anti-malaria benefits. A 2008
study, however, failed to conform the association between exposure and
difficulty breastfeeding

• Several recent studies demonstrate a link between in utero exposure to

DDT or DDE and developmental neurotoxicity in humans. For example, a
2006 University of California, Berkeley study suggests that children
exposed while in the womb have a greater chance of development
problems, and other studies have found that even low levels of DDT or
DDE in umbilical cord serum at birth are associated with decreased
attention to infancy and decreased cognitive skills at 4 years of age.
Similarly, Mexican researchers have linked first trimester DDE exposure
to retarded psychomotor development.

• Other studies document decreases in semen quality among men with

high exposures (generally from IRS)

• Studies generally find that high blood DDT or DDE levels do not increase
time to pregnancy (UP). There is some evidence that the daughters of
highly exposed women may have more difficulty getting pregnant (i.e.
increased UP)

• DDT is associated with early pregnancy loss, a type of miscarriage. A

prospective cohort study of Chinese textile workers found “a positive,
monotonic, exposure — response association between preconception
serum total DDT and the risk of subsequent early pregnancy losses. The
median serum DDE level of study group was lower than that typically
observed in women living in homes sprayed with DDT.

• A Japanese study of congenital hypothyroidism concluded that in utero

DDT exposure may affect thyroid hormone levels and “play an important
role in the incidence and/or causation of cretinism. Other studies have
also found the DDT or DDE interfere with proper thyroid function.
Chlorofluorocarbon

i. INTRODUCTION: Chlorofluorocarbons (CFCs), family of synthetic

chemical that are compounds of the elements chlorine, fluorine, and
carbon. CFCs are stable, nonflammable, noncorrosive, relatively nontoxic
chemicals and are easy and inexpensive to produce. During the 1970s,
scientist linked CFCs to the destruction of Earth’s ozone layer. The
manufacturer of CFCs has since been banned in most countries.

ii. USES: Scientists developed the first CFCs during the late 1920s. the
compounds subsequently became used in a wide range of industrial
products in the United States, Europe, and Japan. Manufacturers used
CFCs as refrigerants in refrigerators, freezers, air conditioners, and heat
pumps, and as propellants in aerosols and medical inhalers. CFCs also
served as inculcating foams in packaging materials, furniture, bedding,
and car seats. Cleaning agents for electronic circuit boards, metal parts,
and dry cleaning processes also used CFCs

iii. HARMFUL EFFECTS: CFCs damage the ozone layer when they escape
from sources such as leaky car air conditions, discarded plastic-foam egg
cartons, and old home air conditioners crushed in a landfill. The CFCs
drift up to the stratosphere, an upper layer of the atmosphere were
strong ultraviolet radiation from the Sun breaks them down. As they
break down, they release chlorine, which depletes the protective ozone
layer. A single chlorine atoms can destroy over 100,000 ozone molecules

Ozone absorbs ultraviolet radiation. When the ozone layer thins,

more of a harmful type of ultraviolet radiation called UVB reaches
Earth’s surface. Studies show that UVB radiation can cause skin cancer.
UVB has also been linked to cataracts of the eye and to suppression of
the immune system. Fish, shrimp, crabs, amphibians, and other animals
that live in or around water — including phytoplankton, microscopic
organisms that form the foundation of aquatic food webs — are all at risk
from UVB radiation.

iv. REGULATION: To combat the problem of ozone thinning, in 1978 the US

Congress banned CFCs used in aerosols in the United States. In 1987,
27 nations signed an international agreement called the Montreal
Protocol, calling for a 50 percent reduction of CFC production by 1998
and an eventual end to all manufacture of CFCs. Later amendments
accelerated the timetable for eliminating CFC production. The Montreal
 Protocol has been remarkably successful in curtailing production of
CFCs. More than 175 nations have ratified the protocol.

Scientists have worked hard to find alternatives to CFCs that spare

the ozone layer. Alterative refrigerant has completed replaced CFCs in
the United States and substantial progress has been made finding
alternatives for foam products and air conditioning. Many of the
alternatives have the added bonus of being highly energy efficient,
helping the United States and other countries meet goals of reduced
global warming emissions.

v. EXTENDED IMPACT: Despite these important steps, previously released

CFCs continue to damage the ozone layer because they can remain in the
atmosphere for more than 100 years. Ozone depletion is particularly bad
over the Antarctic, seasonally producing an ozone hole, a large area of
the atmosphere that contains extremely low amounts of ozone. Low levels
of ozone have also been observed over the United States, Canada, Japan,
Russia, and Europe. Scientists predict that the highest levels of CFCs in
the atmosphere will occur during the first decade of the 2Vt century. If
international agreements hold, the ozone layer is expected to recover
around 2050.

2.0 ALKANOLS

General molecular formula and nomenclature

Alkanols are known to be another example of a homologous series with

general molecular formula: Cn H2n + 10H where n represents the number of
carbon atoms present in the compound.

The hydroxyl group — OH serves as the functional group of the

homologous series. Because this series contains only one hydroxyl group, they
are known as aliphatic monohydric alcohols since they are relative of alkanes.

They may be classified as primary (1°) secondary (2°) ox tertiary (3°)

according to the nature of the carbon atoms to which the hydroxyl groups is
attached
 A primary alcohol has only one carbon, a secondary alcohol two and a
tertiary alcohol three carbons attached to the carbon bearing the — OH group.
Thus we can have the examples given above.

Nomenclature

The IUPAC system is generally adopted for most alcohols, although

common names which are afforded by stating the name of the appropriate alkyl
group followed by the word alcohol are still sometimes used for the simple
compounds e.g. methyl alcohol, is oprophyl alcohol, benzyl alcohol etc.

The IUPAC names are afforded by dropping the ending ‘-ane’ of the
corresponding alkane and replacing it with the suffix ‘ol’ . the position of the
hydroxyl group in the carbon chain is specified by inserting the appropriate
number between the stem of the name and the — ol.

Physical Properties of alcohols

Most simple aliphatic alcohols and the lower aromatic alcohols are
liquids at room temperature, the boiling points of which increase with
increasing relative molecular mass, although branched isomers end to be more
volatile than their straight chain and less high branched counterparts.

Aliphatic alcohols containing more than twelve carbons and the higher
aromatic ones are waxy solid.

The order of boiling points of isomeric alcohols is 10 alcohols> 20

alcohols> 30 alcohol
 The density of the alcohols becomes greater with increasing relative
molecular mass, although branching again has the effect of reducing this
factor. All aliphatic alcohols are less dense than water but the aromatic
homologues tend to be slightly more dense than water.

Simple alcohols possess many properties characteristics of water and

may be regarded as monoalkyl derivatives of water. On the other hand, higher
members exhibit properties which are much more analogous to those of the
hydrocarbons and are better regarded as hydroxyl derivatives of alkanes. for
example methanol, ethanol and propan-l-ol are miseible in water in all
proportions, due largely to their ability to form hydrogen bonds with the water
molecyles, where as higher members show a marked decrease in solubility. The
hydrocarbon nature of hexan-l-ol is indicated by the fact that its solubility at
20°c is only 0.6g in 60g of water.

All alcohols are miscible with most organic solvents and the simple ones
are themselves useful organic solvents.

Industrial Preparation of Ethanol From Ethane

Ethanol is manufactured nowadays mainly by the direct hydrolysis of

ethane. This involves passing a stream of ethane and water vapour over a
phosphoric (v) acid on celite catalyst at a temperature of 300°c and 68-70 atm
pressure.
 Some is still obtained by absorbing ethane in concentrated sulphuric
acid 80°c and 25-30 atm and then hydrolyzing the ethyl sulphate with an equal
volume of warm water, although this technique is gradually becoming
outmoded and will eventually become obsolete.

From Fermentation of Sugar

The fermentation of sugar (carbonhydrates) still provides a useful small

sources of ethanol. The biological catalysts, enzymes, found in the yeast break
down the sugar molecules into ethanol to give a yield which is in the region of
95%.

Glucose is rarely used in practice as some other suitable and cheaper

raw materials is usually available e.g. molasses, potatoes, cereal, rice etc. all of
these materials contain starch (C 6H10O5)n which on warming with malt to 60°c
for a specific period of time is converted into maltose by the enzyme DIASTASE
contained in the malt

2 ( C 6 H 10 0 5)
starch
n
+nH 2 0⃗
diastase nC 12 H 22 011
60 0 c maltose

On the addition of yeast, which contains the enzyme MALTASE, the

maltose is broken into glucose which at a maintained temperature of 15°c is
then converted into alcohol by the enzyme ZYMASE also contained in the yeast.

Industrial alcohol is often rendered poisonous and hence undrinkable by the

addition certain chemicals such as methyl alcohol, pyridine, motor spirit and
coloured dyes. This is known as “DENATURING” the alcohol. Denatured
alcohol is sold under the name of methylated spirit

Industrial & Domestic Use of Alkonols

Alcohols are good starting materials for the preparation of many organic
compounds.

They are relatively cheap, easily available, and the —OH group can be
converted to a large number of other functional groups. The lower members are
good solvent for many substances.

Ethyl alcohol is used for making chloroform, iodo form, vinegar and glacial
ethanoic acid

It is also used as a disinfectant for making various tinctures used in medicine.

3.0 ALKANOIC ACIDS

CARBOXYLIC ACID

SATURATED ALIPHATIC MONOCARBOXYLIC ACIDS form a homologous series

corresponding to the general molecular formula, C nH2+1 COOH, or simple
RCOOH.

Hydroxyl functional group —hence the name. These groups modify each other
to such an extent that the chemical reactivity of the carboxyl group bears little
resemble to either of its constituent groups.

Aliphatic carboxylic acids as a whole are often referred to as ‘fatty’ acids since
several of the higher homologues, notably hexadecanoic (palmitic) acid,
CH3(CH2)14C00H, octadecanoic (stearic) acid CH 3 (CH2)16 COOH, and cis
octadec-9-enoic (oleic) acid, CH3(CH2)7 CH= CH (CH2)7 COOH are constituents of
natural fats and are obtainable from this source.
In terms of the quantity of acid consumed, the most important carboxyllc acid
is without doubt ETHANOIC (ACETIC) ACID.

The simplest of the aliphatic series of dicarboxylic acids are:

NOMENCLATURE

Common names are generally derived from the latin or Greek name of their
source of origin.

FORMIC ACID derives its name from the fact that it is obtainable by distilling
crushed ants (Lat. Formica, ant), although it is also preen tint stinging nettles
and certain other plants.

On exposure to the atmosphere, wines, notably sweet ones with a fairly low
alcohol contain, often become sour and turn to vinegar (French vinaigre, sour
wine) owing to attack by a bacterium, commonly referred to as the ‘vinegar fly’.
This micro-organisms instead of allowing the sugar to be converted into
alcohol, turns it into acetic (ethanoic) acid (lat. Acetum, vinegar)

Name Source Derivation

Propionic acid Plant and animal products Gr. proto (first) pion (fat)
Butyric acid Rancid butter Lat. butyrum, butter

Caproic acid Goat’s mil Lat. caper, goat

Position of substitution in the hydrocarbon chain are donated by the Greet

letter β , etc

IUPAC names are afforded by taking the name of the appropriate alkane and
replacing the ending ‘-e’ with eth suffix ‘-oic’ acid. Positions of substitution are
denoted in the usual way by numbering the longest unbranched chain
containing the carboxyl group.

Formula TUPA C name Common name

HCOOH Methanoic Formic

CH3COOH Ethanoic Acetic

CH3CH2COOH Propanaoic Propionic

CH3(CH2)2COOH Butanoic n-Butyric

(CH3)2CHCOOH 2-methylpropanoic Isobutyric

CH3(CH2)3COOH Pentanoic n — Valeric

CH3(CH2)14C00H Hexadecanoic Palmitic

CH3(CH2)16C00H Octadecanoic Stearic

C6H5CH2COOH 2-Phenylethanoic Phenylacetic

PHYSICAL PROPERTIES
All simple aliphatic acids as far as C 10 are liquids at room temperature,
although anhydrous ethanoic (acetic) acid freezes to an ‘ice-like’ solid below
17°c and is commonly known as glacial ethanoic (acetic) acid. Like all the lower
members, ethanoic acid possesses a sharp, pungent odour.

Boiling points follow the usual pattern of increasing with increasing relative
molecular mass.

Aromatic acids are crystalline solids and have higher melting points than
their aliphatic counterparts of comparable relative molecular mass.

‘Even’ members of the aliphatic series have markedly higher melting

points than ‘odd’ members, and x-ray analysis has shown this to be related to
the packing of the crystals in the solid.

The first four aliphatic acids are completely miscible with water and, as
in the case of the simpler alcohols, this is largely due to the ability of the
functional group to form hydrogen bonds with the water molecules. Because of
their greater hydrocarbon, and hence covalent, character, the higher
homologues become progressively less soluble in water.

Benzenecarboxylic (benzoic) acid is only slightly soluble in cold water but

dissolves readily in hot.

All carboxylic acids can be dissolved in suitable organic solvents.

Density follows a general pattern of decreasing with increasing relative

molecular mass.

REACTIONS OF CARBOXYLIC ACIDS

The main reactions of carboxylic acids may be classified as follows:

(i) Acid behavior involving only the carboxyl hydrogen

(ii) Reactions in which the — OH is replaced by other groups such as — Cl, -
OR (R =Alkyl), - NH2 or — NHR. Products of these reactions are usually
referred to as carboxylic acid derivatives.

(iii) Reduction — in which the — COOH groups is converted to —CH 2OH.

(iv) Decarboxylation — in which the carboxyl carbon is loss as CO 2

Acid Behaviour

When a carboxylic acid dissolves in water the following equilibrium is

established.

RCOOH + H20 RCO0- + H3O+

The equilibrium constant Ka is given by the expression;

Ka = [RCOO] [H30+]

[RCOOH]

The above dissociation, as has been mentioned earlier, is responsible for the
acid behavior of carboxylic acids.

Carboxylic acids are weaker acids than mineral acids. For example the pKa for
ethanoi acid is 4.75. They are however stronger acids than carbonic acid
(H2C03). Thus when a carboxylic acid is added to a saturated solution of
sodium hydrogen carbonate (Na+HCO3) carbonic acid is released and this
decomposes to carbon dioxide and water

A simple test for carboxylic acids therefore is the evolution of carbon dioxide
when the acid is added to a saturated solution of sodium hydrogen carbonate.
(Phenols which are weaker acids when carbonic acid do not give this test)

Carboxylic acids form salts with bases.

Salts of carboxylic acids, being ionic, are soluble in water and insoluble in
either. Organic compounds in general are insoluble in water but soluble in
ether. These differences in solubility are often used to separate organic acids
(or salts of organic compounds) from other organic compounds. For example a
mixture of benxoic acid and the hydrocarbon naphthalene (C 10H8) may be
separated by first dissolving in ether and washing the ethereal solution with
aqueous sodium hydroxide solution. The acids forms a salt and dissolves in the
water layer while the hydrocarbon remains in the ether layer. The two layers
are separated and the carboxylic acid generated by the addition of excess
mineral acid to the water layer. Benzoic acid, being sparingly soluble in water
precipitates out and is filtered. Alternatively the regenerated acid may be
extracted with there and the that evaporated off.

The strength of Carboxylic acid

Two factors determine the strength of carboxylic acids: (a) the ease of
dissociations of the 0 — H bond (b) the stability of the carhoxylate anion
compared with the undissociated molecule. Compared with alcohols the
dissociation of the 0 — H bond in carboxylic acids is facilitated by the
displacement of electrons towards the oxygen atom of the carbonyl group. The
resulting carboxylate anion is also stabilized by resonance.
Although the undissociated acid also shows resonance the two rsonance
structures are non — identical and the structure with the separation of charge
makes less contribution to the stability of the resonance hybrid. Resonance is
in the carboxylate anion however involves 1:wo identical structures with no
charge separation. There is therefore greater resonance stabilization in the
carboxylate anion than in the undissociated.acid. As we noted in the case of
alcohols the dissociation of the 0 — H bond is discouraged by the release of
electrons from the alkyl group (R) and the resulting alkoxide ion is destabilized
by the same effect.
______
R 0______ H + H20 R______ 0 + H30+

Carboxylic acids are therefore much stronger acids than alcohols.

The group attached to the carboxyl group has a significant effect on the
strength of a carboxylic acid. Electron withdrawing groups facilitate
dissociation of the 0 — H bond and stabilize the carboxylate anion by taking
part in the dispersal of the negative charge. This enhances the acidity. The
greater the number of electron — withdrawing groups and the nearer they are
to the carboxyl group the greater the effect on the acidity. Conversely electron
— donating groups decrease the acidity. Compared the pKa’s of the following
acid.
CH3CH2CHCICOOH pKa 2.85

CH3CHCLCH2CO2H “ 4.05

CH2CLCH2CH2COOH “ `4.52

Fluorethanoic acid (CH2FCOOH) containing the most strongly electron

withdrawing halogen to i is the most acidic of the monohaloethanoic acids, with
iodoethanoic acid the least acidic.

4.0 AMINES, AMINO ACIDS AND PROTEINS

AMINES

Amines are compounds containing the amino ( - NH2) group. They may
be considered to L2 derived from ammonia by the replacement of one or more
hydrogens by alkyl or aryl groups. They are classified as primary, secondary
and tertiary on the basis of the number of hydrogens that have bcc replaced.
Primary amines have only one hydrogen of ammonia replaced by an alky or
aryl group. Primary amines therefore have only one alkyl or aryl group,
secondary amines have two, and terUry amines have three. Amines having only
alkyl groups are aliphatic amines, and those with aryl group aromatic amines.
Note the use of primary, secondary, and tertiary here differs from their use
with alcohols. With amines it is the number of groups attached to the nitrogen
that forms the basis for classification; with alcohols it is the nature of the
carbon to which the functional groups (-OH) is attached. Thus, whereas
tertiary butylamine is a primary amine, tertiary butyl alcohol s a tertiary
alcohol.

NAMING OF AMINES

The systematic names of amines are obtained by using the prefix amino with
the name of the parent hydrocarbon, and indicating with numbers the point of
attachment of the amine (-NH2) group to the carbon skeleton. The most
commonly used names however are those obtained by adding amine to the
name(s) of the alkyl or aryl group(s) attached to the nitrogen. There are also
trivial names such as aniline and toluidine.
Note that the prefix N — is used to indicate a substituent group attaché to the
nitrogen atom.

PHYSICAL PROPERTIES OF AMINES

Like other classes of compounds, the boiling point of amines increase

with increasing molar mass. Thus methylamine and ethylamine are gases at
ordinary temperatures and pressures whereas the higher members are liquids,
then solids.

The lower alkylamines are extremely soluble in water (compare the high
solubility of ammonia in water). Solubility decreases with increasing molar
mass, In general the aromatic amines are less soluble in water than the
aliphatic amines of comparable molar mass.

The high solubility of the lower aliphatic amines is due to hydrogen

bonding between the –NH2 group and water molecules. This may be compared
with the high solubility of alcohols in which has also been attributed to
hydrogen bonding between — OH groups and water molecules.

AMINO ACIDS AND PROTEINS

Proteins are found both in plant and animal tissues where they perform
a wide variety of functions. They form part of the structural material such as
the skin, muscle and membranes. Enzymes, hormones, nucleoproteins, blood
and plasma proteins, which take part in physiological processes are examples
of protein.

Plants can synthesise proteins from carbon dioxide, water, and nitrogen
but animals cannot. Animals therefore depend on plants and other animals for
their protein supply.

Proteins have large molecular weights (10,000 — 10,000,000) and highly

complicated structures, and like polysaccharides are polymers, the building
blocks of which are amino acids. Unlike polysaccharides however which are
built from only one type or only few monosaccharides, protein molecules are
built from about twenty different amino acid.

Amino acids are compounds containing both carboxyl (-COOH) and amino (-
NH2) groups. They therefore have both acidic and basic properties. The amino
group may occupy any position on the carbon skeleton and there may be more
than one in the molecule. All amino acids which occur in nature (i.e. obtained
from the hydrolysis of proteins) have the amino group in the alpha position.
They are therefore called a —amino acids. Where there are more than one
amino group the others are attached to the omega (or last) carbon atom. Such
amino acids are known as basic amino acids. There are other amino acids
which have more than one carboxyl groups. These are known as acidic amino
acids.

Thus in an electric field the amino acid molecule may migrate to th

epositive or negative pole depending on the pH of the medium. At some pH,
which is different for different amino acids, there is no migration to either pole
since the molecule then exists predominantly as the double ion. This pH is
called the isoelectric point of the amino acid. This behaviour of amino acids in
an electric field is used in electrophoretic separation of amino acids and
proteins. Table above show some commmon amino acids and their isoelctric
points.
Reactions

The reactions of aminoethanoic acid are typical of a compound containing both

an amino and a carboxyl group.

In solution, it exists in equilibrium with its tautomer, a dipolar ion or Zwitter!on

(literally “between ion’), formed by the intramolecular migration of the addic
proton.

The equilibrium lies very much towards the right-hand side, and the
amphoteric nature of this species is illustrated by the fofwing scheme, showing
is relative stability in both acidic and basic media.

In acidic media, aminoethanoic acid exists as the cation, NH 3CH2COOH,

Whereas in a basic medium it functions asthe anion, NH 2CH2COO. At the
intermediate point, the dipolar ion possesses no net charge and this position is
referred to as the ISOELECTRIC POINT.

The acidic and basic strengths of aminoethanoic acid are extremely low
compared with those of carboxylic acids and most aliphatic amines.

Aminoethanoic acid, pKa = 987 (cf ethanoic acid pKa = 4.76)

Aminoethanoic acid. PKb = 4.13 (cf methylamine, PKb = 3.36)

5.0 SYNTHETIC MACRO MOLECULLS

POLYMERS — PLASTICS

A polymer is a large molecule formed by the repeated combination of a

large number of small molecules or monomers. Polymers may be divided into
two main groups — natural (or biological) polymers and synthetic (or non-
biological) polymers. natural polymers are made by livinq. organisms, and
include such substances as starch, cellubse, proteins, and natural rubber.
Synthetic polymers are made by man, and include things like polythene,
polystyrene, nylon, plastics and synthetic rubber.

The uses of polymers are many and varied. Both natural and synthetic
polymers are used as fibres for making textiles, ropes, sheet and wrappers. In
addit’on, synthetic polymers are used for making such objects as buckets and
containers of various types, plates, cups, water-hoses, electrical insulators,
water-pipes, tubings, buttons, combs and toys:

The synthetic materials are so widespread today that they have replaced
many of the materials traditionally used by man. This success of synthetic
materials is due to number of advantages they enjoy over the natural
materials. For example some of them are light but tough, unbreakable, flexible,
elastic, water-proof, unaffected by chemicals, and bad conductors of electricity
and heat. Although synthetic materials may not be all that cheaper than the
natural ones, their preference may be due mainly to these properties. Synthetic
moterials however suffer one big disadvantage — that of disposal. Since these
materlais are not attacked by insects and microorganisms they do not rot, and
their disposal therefore poses a big environmental problem.

SYNTHETIC POLYMERS

Synthetic polymers are used commercially and dornsticaliy in three main

forms — as elastomers; fibres and plastics. elastomers have elastic properties
that is, they stretch when pulled, but resume their origmal shape when
released. Fibres used for making textiles, fishing nets and ropes have a high
tensile strength. Plastics on the other hand show a wide variety 9f properties,
such as flexibility toughness, good insulation, resistance of chemicals and
weather. Plastics are substances which can be moulded when they are soft and
pliable (Le. plastic) but which can be treated after moulding into rigid objects.

Synthetic polymers are produced by two tyes of polymerization the

simple molecule (monomers) usually containing a double bond join up to form
large polyme molecules with the disappearance of the double bonds For
example, molecules of ethane polymerize by addiUon reactions to give
polythene.

In condensation polymerization, the monomers combine to form

polymers with the elimination of water or some other small molecule. For
example in the formaUoh of Bakelite two molecules of phenoi are llnked by a
molecule of methanol with the elimination of molecule of water.

Neoprene rubbers a polymer dl chloOprene (2-:hIoro1-3-butadiene and sWrene

with sodiem as cata!yst, Buna S is thus an abbrevfation for botadiene-Na-
Styrene.
VULCANIZATION

Vulcanization is the process whereby rubber is heated with sulphur to toughen

it. The sulhur reacts with the rubber to form crosslinks between the polymer
molecules. This treatment improves the qualities of the ruhber. Raw rubber
has a low tensile strength, is not very elastic, is softens on heating, and tends
to stick to other materials. Vulcanized rubber, on the other hand has high
tensile strength, is very elastic, not very sensitive to heat and is not sticky